3-methyl-4-trimethylsilylcyclobutene-1,2-dione | 154473-78-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 3-methyl-4-trimethylsilylcyclobutene-1,2-dione
• 英文别名: 3-methyl-4-trimethylsilyl-3-cyclobutene-1,2-dione；3-Methyl-4-trimethylsilylcyclobut-3-ene-1,2-dione
• CAS: 154473-78-6
• 化学式: C₈H₁₂O₂Si
• 分子量: 168.268
• InChiKey: PNFLWRDOZITZCV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.14
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-methyl-4-trimethylsilylcyclobutene-1,2-dione 以55%的产率得到
  参考文献：
  名称：

  Formation and Reactivity of Unsymmetrical Bis(ketenes): 2-Phenyl- and 2-Methyl-3-(trimethylsilyl)-1,3-butadiene-1,4-diones

  摘要：

  DOI：

  10.1021/ja00085a055
• 作为产物：
  描述：

  以 异辛烷 为溶剂， 生成 3-methyl-4-trimethylsilylcyclobutene-1,2-dione
  参考文献：
  名称：

  通过闪光光解和闭环动力学从环丁烯-1,2-二酮生成 1,2-双烯酮1a

  摘要：

  环丁烯-1,2-二酮 (1) 和 1,2-双烯酮 (RCCO)2 (2) 的相互转化已针对不同的取代基组合 R = H、Me、t-Bu、Ph、Me3Si、CN、 Cl、Br、R1O、炔基和PhS。双烯酮 2 是通过闪光光解产生的，并且通过时间分辨红外和紫外光谱研究了它们转化为 1 的动力学。2 的闭环速率常数与乙烯酮稳定参数 (SE) 和计算的势垒相关。二叔丁基双烯酮 2g 至环丁烯二酮 1g 的闭环速率常数仅比二甲基类似物小 40 倍，显示出相当适中的空间位阻。quinoketene 2s 的闭环速度很快，但没有根据计算的几何和热力学因素预期的那么快。

  DOI：

  10.1021/ja9722685

文献信息

• Reactive Iron Carbonyl Reagents via Reaction of Metal Alkoxides with Fe(CO)₅ or Fe₂(CO)₉: Synthesis of Cyclobutenediones via Double Carbonylation of Alkynes
  作者：Mallesh Beesu、Mariappan Periasamy

  DOI：10.1021/jo102104a

  日期：2011.1.21

  Alkoxy bases such as t-BuOK react with Fe(CO)5 to give reactive iron carbonyl intermediates that in turn react with alkynes at 70 °C in THF to give 1,2-cyclobutenediones in 70−93% yields after CuCl2·2H2O oxidation. A novel 1,2-diacyloxyferrole derivative was isolated in the reaction of diphenylacetylene with Fe(CO)5/t-BuOK in the presence of acetyl chloride in contrast to the formation of a 1,4-diacyloxyferrole

  烷氧基碱（例如t -BuOK）与Fe（CO）5反应，生成反应性羰基铁中间体，然后在THF中与炔烃在70°C下反应，在CuCl 2 ·2H后以70-93％的产率生成1,2-环丁烯二酮2 O氧化。在二苯基乙炔与Fe（CO）5 / t- BuOK在乙酰氯存在下的反应中，分离了一种新型的1,2-二酰氧基铁络合物，与使用Fe的反应中形成的1,4-二酰氧基铁络合物形成了对比（CO）5 / Me 3 NO。铁2（CO）9 /吨-BuOK试剂系统还可以在类似的反应条件下，以63-90％的产率将炔烃转化为相应的环丁二烯。
• <i>tert</i>-Butyl Substituent as a Regiodirecting and Novel C−H Protecting Group in Cyclobutenedione-Based Benzannulation Chemistry
  作者：Fuqiang Liu、Lanny S. Liebeskind

  DOI：10.1021/jo971565p

  日期：1998.5.1

  2-Unsubstituted hydroquinone monoacetates, quinones, and 3-unsubstituted quinolizinones were synthesized in moderate to high yields via tert-butyl and trimethylsilyl substituted cyclobutenediones. The addition of unsaturated carbon nucleophiles proceeded regiospecifically at the carbonyl group most distant from the tert-butyl or trimethylsilyl substituent. Thermolysis of the adducts, followed by treatment under acidic conditions to remove the tert-butyl and trimethylsilyl groups in good overall yields, provided access to a variety of "less-substituted" hydroquinone monoacetates, quinones, and quinolizinones. Of the two systems, the tert-butyl-substituted cyclobutenediones proved the most useful.
• Spiro-Aziridine and Bislactam Formation from Bisketene−Imine Cycloadditions
  作者：Annette D. Allen、Jazmin Godoy、Nanyan Fu、Michelle Nagy、Sandra Spadaro、Thomas T. Tidwell、Sinisa Vukovic

  DOI：10.1021/ja077623y

  日期：2008.2.1

  1,2-Bisketenes 6 react with imines PhCH=NAr, (E)-2, forming spiro-aziridines 7. DFT computations indicate that this occurs by nucleophilic attack of the imine on the carbonyl carbon of the more reactive arylketene moiety, followed by cyclization, and not by prior cyclization of the 1,2-bisketene forming a carbene lactone intermediate. Computations also indicate that the previously studied bisketene 10 from benzocyclobutadiene 9 is 4.0 kcal/mol less stable than carbene lactone 12 that would result from cyclization but that the failure to observe 12 results from a lower barrier for 10 to instead revert to 9. 1,2-, 1,3-, and 1,4-Bisketenylbenzenes 16, 19, and 22 react with imines forming bis(beta- lactams), with a preference for formation of mixtures of trans, trans chiral (+/-) and achiral diastereomeric products.
• Allen Annette D., Lai Wing-Yan, Ma Jihai, Tidwell Thomas T., J. Amer. Chem. Soc, 116 (1994) N 6, S 2625-2626
  作者：Allen Annette D., Lai Wing-Yan, Ma Jihai, Tidwell Thomas T.

  DOI：——

  日期：——